Isomerization of allylic and homoallylic alcohols is catalyzed by the zwitterionic Rh(I) complex (sulphos)Rh(cod) in water-n-octane to give the corresponding aldehyde or ketone in high yields and chemoselectivity. A pi -allyl metal hydride mechanism is proposed on the basis of various independent experiments in both homogeneous and biphasic systems [ sulphos = -O3S(C6H4)CH2C(CH2PPh2)(3)].
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